ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 11, pp. 1846–1854. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © A.S. Burlov, A.S. Antsyshkina, G.G. Sadikov, V.S. Sergienko, A.I. Uraev, E.V. Korshunova, D.A. Garnovskii, T.V. Lifintseva,
G.S. Borodkin, A.G. Ponomarenko, G.G. Chigarenko, I.L. Eremenko, 2012, published in Zhurnal Obshchei Khimii, 2012, Vol. 82, No. 11, pp. 1856–1864.
1846
Syntheses, Structure, and Tribological Study
of 1-Phenyl-3-methyl-4-dodecyliminomethylenepyrazol-5-one
and Its Complexes with Copper(II)
A. S. Burlov
a
, A. S. Antsyshkina
b
, G. G. Sadikov
b
, V. S. Sergienko
b
, A. I. Uraev
a
,
E. V. Korshunova
a
, D. A. Garnovskii
c
, T. V. Lifintseva
d
, G. S. Borodkin
a
,
A. G. Ponomarenko
e
, G. G. Chigarenko
e
, and I. L. Eremenko
b
a
Research Institute of Physical and Organic Chemistry, Southern Federal University,
pr. Stachki 194/2, Rostov-on-Don, 344090 Russia
e-mail: garn@ipoc.rsu.ru
b
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia
c
Southern Scientific Center, Russian Academy of Sciences, Rostov-on-Don, Russia
d
Pedagogical Institute of Southern Federal University, Rostov-on-Don, Russia
e
Scientific Industrial and Commercial Company “Don-Invek,” Rostov-on-Don, Russia
Received August 18, 2011
The metal complexes of azomethine compounds
occupy an important place in modern coordination
chemistry [1–5] and are used as fluorescent [6–9],
magnetic [10–14], catalytic [15] and optical materials
[16–18]. They are used also as effective additives to
lubricants [19–30]. The development of the latter is an
important and urgent task.
At the metal friction in an environment with
complex-forming additives both chemical and
tribochemical interactions occur, giving rise to the
appearance on the surface of complex compounds
formed from the contacting metal and ligand-additives
[19–28]. Further a tribochemical processes of the
complex exchange proceed: on both the rubbing
surfaces a thin polymer film is formed of copper or
other complex-forming transition metal. Therewith a
process occurs of selective transfer, which leads to a
significant improvement of tribochemical charac-
teristics [31]. The effectiveness of the additives is
determined by their solubility in oils, structure of the
metal complexes formed, and the stability of the latter
[19, 20]. To fix the metal complex on the rubbing
surface, the complex coordination sphere should have
a structure that minimizes the steric strains at the
location of the complex in the active points of
frictional contact. The steric hindrances at the location
of the complex on the friction surface reach minimum
when the complex has a square structure. Thus, at the
selection of effective additives for lubricants the
knowledge of the structure and properties of metal
complexes is an important issue.
In extension of the work on the synthesis of new
effective additives for lubricants we have prepared
1-phenyl-3-methyl-4-dodecyliminomethylenepyrazol-
5-one (HL) and its copper complex CuL
2
(I).
In the compound HL the equilibrium of the A–D
tautomers can be realized [32–34]. The IR spectrum of
the HL solution in hexachlorobutadiene includes the
following absorption bands: a broad band at 3420 cm
–1
(ν
NH
) and a strong band at 1668 cm
–1
(ν
C=O
).
The presence of a broad signal of the protons of NH
group in the
1
H NMR spectrum of HL in CDCl
3
at
09.07 ppm and a doublet signal at 7.43 ppm of the
(CH –NH) protons in combination with the IR spectral
studies and published data [32–34] indicate the
existence of HL in aminomethylene tautomeric form B
with the intramolecular hydrogen bond with the
oxygen atom of the pyrazole fragment.
In the IR spectrum of the Cu(I) complex the
absorption bands of HL at 3420 and 1668 cm
–1
dis-
DOI: 10.1134/S1070363212110217